Preparation of hydrazidines

Abstract

A new one-step process for the preparation of hydrazidines of the general formula <IMAGE> (I) in which R represents an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, or their acid addition salts, in high yield comprises reacting iminoalkyl ethers of the general formula <IMAGE> (II) in which R has the abovementioned meaning and R1 represents an optionally substituted alkyl group or an optionally substituted cycloalkyl group, or their acid addition salts, with hydrazine in solvents under reduced pressure and at temperatures between -80 DEG and +100 DEG C., the reaction being effected in the presence of water present in the solvent and/or in the hydrazine by employing it as hydrazine hydrate. The hydrazidines of formula (I) and their salts are valuable intermediates in heterocyclic chemistry, for example for the synthesis of herbicidally active as-triazinones.

We claim: 
     
       1. In the production of a hydrazidine of the formula ##STR8## in which R is an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, or an acid addition salt thereof, by reacting the corresponding iminoalkyl ether of the formula ##STR9## in which R 1  is an optionally substituted alkyl group or an optionally substituted cycloalkyl group,   or an acid addition salt thereof, with hydrazine in a solvent, the improvement which comprises effecting the reaction using hydrazine hydrate in the presence of an inert organic solvent under reduced pressure and at a temperature between about -80° and +100° C.   
     
     
       2. A process according to claim 1, wherein the solvent contains about 0.1 to 20% of water. 
     
     
       3. A process according to claim 1, wherein the pressure ranges from about 0.1 to 800 mbar. 
     
     
       4. A process according to claim 1, wherein the temperature is between about -30° and +50° C. 
     
     
       5. A process according to claim 1, wherein about 2 to 2.5 mols of hydrazine hydrate are employed per mol of the iminoalkyl ether acid addition salt thereof. 
     
     
       6. A process according to claim 1, in which R is an optionally substituted alkyl group with 1 to 12 carbon atoms, an optionally substituted cycloalkyl group with 3 to 6 carbon atoms, an optionally substituted aryl group with 6 or 10 carbon atoms or an optionally substituted aralkyl group with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part. 
     
     
       7. A process according to claim 1, in which R is a methyl, chloromethyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl group. 
     
     
       8. A process according to claim 1, in which R 1  is an optionally substituted alkyl group with 1 to 12 carbon atoms or an optionally substituted cycloalkyl group with 3 to 6 carbon atoms. 
     
     
       9. A process according to claim 1, wherein the iminoalkyl ether is selected from the group consisting of acetiminoethyl ether, chloroacetimonoethyl ether, trichloroacetiminomethyl ether, trichloroacetiminoethyl ether, propioniminoethyl ether, butyriminoethyl ether, valeriminoethyl ether and the hydrochlorides thereof. 
     
     
       10. A process according to claim 1, wherein the reactants are acetiminoethyl ether hydrochloride and hydrazine hydrate. 
     
     
       11. A process according to claim 10, about 2 to 2.3 mols of hydrazine hydrate being employed per mol of iminoethyl ether, the solvent containing about 0.1 to 20% of water, the temperature ranging from about -30° to +50° C. and the pressure ranging from about 50 to 300 mbar.